CN101298690A - Anodizing aluminium and alloys thereof - Google Patents
Anodizing aluminium and alloys thereof Download PDFInfo
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- CN101298690A CN101298690A CNA2007101020534A CN200710102053A CN101298690A CN 101298690 A CN101298690 A CN 101298690A CN A2007101020534 A CNA2007101020534 A CN A2007101020534A CN 200710102053 A CN200710102053 A CN 200710102053A CN 101298690 A CN101298690 A CN 101298690A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12993—Surface feature [e.g., rough, mirror]
Abstract
This invention encompasses methods of producing a colored oxide layer on an aluminum material by anodizing the aluminum material in an electrolyte comprising water, sulfuric acid and oxalic acid. The anodizing step comprises passing at least two sequential current densities through the electrolyte. Methods of making and using article with a colored oxide layer on an aluminum material make by the methods disclosed herein are also disclosed.
Description
Technical field
[0001] present invention resides in the method that produces colored oxide layer on the aluminum.Particularly, present invention resides in electrolytic solution inner anode oxidation (anodizing) aluminum that contains sulfuric acid and oxalic acid to produce the method for colored oxide layer.
Background technology
[0002] known aluminium and its alloy have many useful performances, as light weight, intensity height, tool weather resistance and casting elasticity.In 1889, Alcoa, Inc. obtains a United States Patent (USP) (being U.S. Patent number 400,664) with an electrolytic process that produces aluminium from aluminum oxide, and apparent the landing of this process reduced the manufacturing cost of aluminium.Afterwards, because all beneficial characteristics and nominal price, aluminium and its alloy are widely used for example aviation, traffic, building, semi-conductor and electronics on many industries.Therefore, in the whole world, the use of aluminium has all surpassed deironing other metal in addition on consumption and value.
[0003] some purposes of aluminum metal and alloy comprise part or the parts of making various products, for example wrist-watch, computer (as the scatterer of CPU), computer related products (as hard disk, flash drive (flash drive), DVD dish etc.), TV, receiving set, refrigerator, air-conditioning system, the vehicles (automobile, aircraft, lorry, train, ship, bicycle etc.), wrapping material (as jar, paillon foil etc.), building products (as window, door, wallboard, electric wire for building etc.), kitchen utensils, electric wire, MKM steel and alnico magnet etc.
[0004] except beneficial characteristics such as above-mentioned, aluminum metal and alloy can be by erosion resistance, abrasion resistance, insulativity, adhesion and/or the aesthetic property of anodic oxidation to promote them.In general, anodic oxidation is an electrochemical process, can be increased in the thickness or the intensity of the aluminium oxide layers of natural generation on the aluminum or aluminum alloy surface.By zone of oxidation or the anode film that sunization produced, according to different manufacturing processedes, can be the high material of hardness second known to the mankind, its hardness may be only after diamond.In general zone of oxidation has the porous structure, and (secondary infusion) (being organic and inorganic coloring, lubricant etc.) injected as finishing in the tolerable second stage.
[0005] process of alumilite process can comprise in batches (batch), continuous coil (continuous coil), continuous member (continuous parts) and basket anodic oxidation (basket anodizing) process.These anode oxidation process not only on the ornamental or protectiveness film of the multiple color that forms, can match in excellence or beauty other as spray paint, japanning and physical vapor evaporation (physical vapor deposition; PVD) etc. technology also can provide unexistent technical advantage of many other technology and benefit.For example, spray paint and paint in general not durablely, and may not meet European Union and limit the use of instruction (Restriction of Hazardous Substances Directive (RoHS)) for the hazardous substance that limits heavy metal and toxic substance and issue.In addition, the PVD process in some cases possibly required color can't be provided and when volume production required process stability.
[0006] developed at present and many anode oxidation process.General anode oxidation process mainly contains three kinds, i.e. chromium anodic oxidation, sulphuric acid anodizing and hard film (hardcoat) anodic oxidation.Described anode oxidation process has description in " anodic oxidation of aluminium alloy and painted " ASM International of S.Kawai (2002) one books, incorporate this specification sheets at this into way of reference.
[0007] the chromium anodic oxidation is commonly referred to first type (Type I) anodic oxidation.It can comprise the electrolyte solution of chromic acid, temperature is about 40 ℃, the about 0.15-0.45A/dm of current density
2Condition under carry out.Described process usually need about 40-60 minute.In general the chromium anodic oxidation can produce the zone of oxidation of an about 1-2.5 micron of thickness.Since the corrodibility of chromic acid than sulfuric acid a little less than, the chromium anodic oxidation can be used to handle comparatively complicated, and the parts that are difficult to clean.The chromium anodic oxidation is compared with described other method of this specification sheets, more can not reduce the fatigue strength of aluminium.
[0008] sulphuric acid anodizing is commonly referred to second type (Type II) anodic oxidation.It can comprise vitriolic electricity matter solution, temperature about 25 ℃ and the about 1.0-1.5A/dm of current density
2Condition under carry out.Described process usually need about 30-60 minute, depends on employed alloy.In general the Chrome anodic oxidation can produce the zone of oxidation of an about 10-14 micron of thickness.Second type specifies (Type II designation) to represent sulphuric acid anodizing, and the first kind (Class 1) under second type is specified is then represented natural colour or do not contained dyestuff, and second class (Class 2) is then represented a kind of dyestuff.
[0009] hard film (hardcoat) anodic oxidation is commonly referred to the 3rd type (Type III) anodic oxidation.In general the zone of oxidation of the 3rd type produces under low-down temperature and high current density.For example, the 3rd type anodic oxidation can be at vitriolated electrolyte solution, at the about 0-5 of temperature ℃ and the about 3.5-4.0A/dm of current density
2Condition under carry out.Described process takes about 20-120 minute usually.In general the hard film anodic oxidation can produce the zone of oxidation of an about 30-60 micron of thickness.
[0010] though described anode oxidation process provides the unexistent advantage of other technologies and the ornamental zone of oxidation with one or more colors is provided under the situation without dyestuff, these anode oxidation process as first type and the 3rd type still have some shortcomings.For example, in general the 3rd type anode oxidation process can produce hard and opaque zone of oxidation, makes it be difficult for the process that dyes and polish.In addition, the zone of oxidation that produced of the second type anode oxidation process may all be not enough to as decorative applications aspect hardness and/or the glittering degree.In addition, the second type anodic oxide coating may dissolve in acrid anodic oxidation water-bath, and the second type thickness of oxide layer is restricted.Even at thicker workpiece (workpiece), when its etching problem was so not serious, corrosion still may make the surface of zone of oxidation become coarse and produce surface imperfection, drips, Fu Erosion groove and analogue as current mark, Tears.
[0011] spray paint in order to overcome, the above-mentioned shortcoming of japanning, PVD and conventional anodization technology; at this process for treating surface that needs to improve aluminum is arranged; so that hard and durable to be provided; can be colored and do the anodized surface of mirror process, to use as various ornamental and/or protectiveness.
Summary of the invention
[0012] the invention provides a method that on aluminum, produces a colored oxide layer, comprise with two kinds of different described aluminums of current density anodic oxidation.Embodiment disclosed in this invention is believed can satisfy above demand.According to an aspect, the invention provides the method that on aluminum, produces a colored zone of oxidation, comprise following steps:
(a) placing described aluminum comprises in water, oxalic acid, the vitriolic electrolytic solution as anode in one; With
(b) the described aluminum of anodic oxidation is less than about 0.8A/dm with current density earlier
2The described aluminum of first galvanic anode oxidation about 1-60 minute; Again with the about 1.5-2.5A/dm of current density
2Second described aluminum of galvanic anode oxidation, to produce a zone of oxidation.
[0013] in some embodiment, described aluminum is about 1.0-1.5A/dm by current density further
2The 3rd galvanic anode oxidation.In other embodiments, described first, second, third electric current produced by Constant Direct Current electric current or pulse direct current electric current respectively.
[0014] in some embodiment, described method further comprises the step that stirs described electrolytic solution with an agitator.In other embodiments, described agitator comprises several mixing drums (agitation tubes).
[0015] in some embodiment, described method further is included in the step that forms a dye coating on the described zone of oxidation.In other embodiment, described electrolytic solution further comprises the mixture of aluminum ion, metal sulfate, the above article of organic acid.In other embodiments, described electrolytic solution further is included in the aluminum ion of about 2-11 gram in every liter of electrolytic solution.
[0016] in some embodiment, described electrolytic solution is included in the oxalic acid of about 5-40 gram in every liter of electrolytic solution and about 100-360 gram sulfuric acid in every liter of electrolytic solution.In other embodiment, described electrolytic solution be included in every liter of electrolytic solution about 12-20 gram oxalic acid and in every liter of electrolytic solution about 140-220 restrain sulfuric acid.In other embodiments, described electrolytic solution be included in every liter of electrolytic solution about 14-18 gram oxalic acid and in every liter of electrolytic solution about 160-200 restrain sulfuric acid.
[0017] in some embodiment, described anodic oxidation step is carried out under about 5-25 ℃ temperature.In other embodiments, described anodic oxidation step is carried out under about 10-15 ℃ temperature.
[0018] in some embodiment, described aluminum comprises aluminium and an element of optionally being chosen, and described element is selected from the group of being made up of the mixture of silicon, boron, germanium, arsenic, antimony, tellurium, copper, magnesium, manganese, tin, lithium, iron, chromium, vanadium, titanium, bismuth, gallium, tin, lead, zirconium, nickel, cobalt and above element.
[0019] in yet another aspect, the invention provides an object, described object comprises an aluminum, contains a colored oxide layer on described aluminum, and the preparation method of wherein said zone of oxidation comprises following steps:
(a) placing described aluminum comprises in water, oxalic acid, the vitriolic electrolytic solution as anode in one; With
(b) the described aluminum of anodic oxidation is less than about 0.8A/dm with current density earlier
2The described aluminum of first galvanic anode oxidation about 1-60 minute; Again with the about 1.5-2.5A/dm of current density
2Second described aluminum of galvanic anode oxidation, to produce a zone of oxidation.
[0020] in some embodiment, described colored oxide layer has the micron hardness value of about 280-1000Hv.In other embodiment, described colored oxide layer has the thickness of about 15-50 micron.In other embodiments, described object further comprises a dye coating on zone of oxidation.In some embodiment, the surface of described colored oxide layer has the Ra value of about 0.01-0.1 micron.
Description of drawings
[0021] Fig. 1 shows an anodic oxide coating on aluminum base layer, and wherein said anodic oxide coating comprises anode unit, and each anode unit all has a hole.
[0022] Fig. 2 shows surface color and the gloss of embodiment 1, comparative example D and comparative example E.
Definition
[0023] in this manual, metal or alloy of " pure substantially " metal finger, it does not contain one or more other elements or compound substantially, as, the content of a metal or an alloy is more than 80wt.%, more than 90wt.%, more than 95wt.%, more than 96wt.%, more than 97wt.%, more than 98wt.%, more than 99wt.%, more than 99.5wt.%, 99.6wt.%, more than 99.7wt.%, more than 99.8wt.%, or more than 99.9wt.%; Or the content of one or more other elements or compound is less than 20wt.%, is less than 10wt.%, is less than 5wt.%, is less than 3wt.%, is less than 1wt.%, is less than 0.5wt.%, is less than 0.1wt.%, or is less than 0.01wt.%.Above-mentioned content is based on the gross weight of described metal or alloy.
[0024] in this manual, " do not contain " element or compound substantially, the content that means described element in the metal or alloy or compound is less than 20wt.%, is less than 10wt.%, is less than 5wt.%, is less than 4wt.%, v3wt.%, be less than 2wt.%, be less than 1wt.%, be less than 0.5wt.%, be less than 0.1wt.%, or is less than 0.01wt.Above-mentioned content is based on the gross weight of described metal or alloy.
[0025] in this manual, alloy is meant by two kinds or the above material that metal constituted.In general, the design of alloy and manufacturing are in order to have some specific target capabilities, to comprise intensity, shaping degree and anticorrosive degree.
[0026] in this manual, Ra is the calculation Intraoperative average deviation of coarse profile (roughness profile) absolute value of average line or center Line, also be called center Line average boldness (centerline average roughness, CLA).Medullary ray is divided profile, make all last area be equal under area.
[0027] in this manual, Rq is root-mean-square value or what average deviation of Few by the coarse profile of the resulting average line of measure sample length.
[0028] in this manual, " polishing " (buffing) or " polishing " (polishing) represent the process that makes workpiece surface become level and smooth, bright, mirror-smooth process for example becomes the surface of metal or alloy.
[0029] below in the explanation of embodiment, all disclosed numerals are all approximation, and no matter whether digital front has " pact " or wordings such as " probably ".These numerals can have 1%, 2%, 5% or the variation of 10-20% sometimes.As the lower limit (R that discloses a digital scope
L) or the upper limit (R
U) time, any numeral in this digital scope also is disclosed.Particularly, the numeral in following scope is disclosed especially: R=R
L+ k* (R
U-R
L), wherein k is a parameter, and variation range from 1% to 100% increases with 1% amplitude, that is and, k is 1%, 2%, 3%, 4%, 5% ..., 50%, 51%, 52% ..., 95%, 96%, 97%, 98%, 99% or 100%.In addition, any defined numerical range of R numerical value by two above-mentioned definition also is disclosed especially.In this manual, all also represent the numerical range of " the about x of clump is to about y " with " about x-y " defined numerical range.
Embodiment
[0030] the present invention discloses some produce colored oxide layer on aluminum method, comprises following steps: (a) place described aluminum and comprise in water, oxalic acid, the vitriolic electrolytic solution as anode in one; (b) the described aluminum of anodic oxidation is less than 0.8A/dm with current density earlier
2The described aluminum of first galvanic anode oxidation from about 1 minute to about 4 hours; Then with 1.5-2.5A/dm
2Second current density produce a zone of oxidation.
[0031] the present invention also discloses the object that some comprise aluminum, have colored oxide layer on the described aluminum, the preparation method of wherein said zone of oxidation comprises following steps: (a) place described aluminum and comprise in water, oxalic acid, the vitriolic electrolytic solution as anode in one; (b) to be less than 0.8A/dm
2The described aluminum of the first current density anodic oxidation about 1-60 minute; Then with about 1.5-2.5A/dm
2The described aluminum of the second current density anodic oxidation to produce a zone of oxidation.In some specific embodiment, zone of oxidation is coloured.In other embodiments, zone of oxidation is opaque and coloured.In further embodiments, zone of oxidation is transparent and coloured.
[0032] described object can be made into or as the part or the parts of many products, for example pen, lighter, wrist-watch, computer, computer related products (as hard disc, flash drive (flashdrive), DVD dish etc.), printer, photoprinter, facsimile recorder, TV, receiving set, refrigerator, air-conditioning system, the vehicles, wrapping material, building products, kitchen utensils, building decorative, machinery or any need hard aluminized decorate properties and the field of specific physicals.
[0033] aluminum that is applicable to the method disclosed in the present and object can be the aluminum metal that does not contain other elements or compound substantially, or any aluminium alloy known in the art.Though aluminum metal all is suitable in many application, on some is used, aluminium alloy since its chemistry, physics and mechanical property by modified, therefore more suitable than aluminum metal.In general, aluminium alloy can be mixed and made into aluminium and other element via heating power-mechanical process.Document about alloy and manufacturing technology thereof can be shown " aluminium and aluminium alloy " ASM International, (1993) with reference to Joseph R.Davis; Show " Technology Innovation inAluminium Products, " with R.E.Sanders
The Journal of The Minerals, 53 (2), pp.21 25 (2001).Two parts of files are intactly included this specification sheets all by reference in.
[0034] in general, aluminium alloy shows improved mechanical property, and high strength is for example particularly passed through the aluminium alloy of temper (tempered).Though many metallic substance also generally are called " aluminium ", in fact they all are aluminium alloys.For example, most aluminium foil all is the aluminium alloy of the about 92-99wt.% of aluminium content.
[0035] in some embodiment, aluminum is the aluminum metal that does not contain the mixture of other element such as copper, Xin, Magnesium, Manganese, silicon, lithium, Tie, Chrome, Vanadium, TA , Gallium , Zirconium or above article substantially.In certain embodiments, aluminum comprises aluminium more than about 95wt.%, more than the aluminium of about 96wt.%, more than the aluminium of about 97wt.%, more than the aluminium of about 98wt.%, more than the aluminium of about 99wt.%, more than the aluminium of about 99.5wt.%, more than the aluminium of about 99.9wt.% or more than the aluminium of about 99.99wt.%, based on the gross weight of aluminum.In certain embodiments, aluminum comprises more than about 99wt.% or more aluminium, based on the gross weight of aluminum.In some infinite embodiment, aluminium comprises the aluminum metal of 1000 series (1000series), for example 1060 and 1100 in the following table 1.
[0036] in other embodiments, used aluminum is an aluminium alloy.Aluminium can be easily forms alloy with the mixture of semi-metal, metal or above metal.In some infinite embodiment, suitable semi-metal comprises silicon, boron, germanium, Shen, Antimony, tellurium and approximate thing.In some infinite embodiment, suitable metal comprises copper, Xin, Magnesium, Manganese, lithium, Tie, Chrome, Vanadium, TA , Gallium , Zirconium and approximate thing.In general, copper can increase intensity, hardness and the thermal treatment degree of alloy; Magnesium can increase tensile strength, resislance to corrosion from sea water, Weldability and the hardness of alloy; Manganese can increase the intensity and the erosion resistance of alloy; Silicon can reduce the fusing point of alloy and promote castability; Intensity and the hardness that can promote alloy with zinc.
[0037] many different tissues are classified to aluminium alloy.For example, some common aluminum alloy composition have been registered in aluminium association (Aluminum Association).On the other hand, many other tissues have been announced comparatively certain criteria, and the manufacturing of standard aluminium alloy comprises American Institute of Mechanical Engineers (Society of Automotive Engineers) normal structure and American Society for testing and materials (ASTM).In addition, the also available tricks type families of aluminium alloy system classification (as ANSI) or with their main alloy compositions name class (as DIN and ISO).
[0038] the used aluminium alloy of the present invention can comprise aluminium and non-aluminium component, and described non-aluminium component comprises at least one or a plurality of semi-metal and other metals.In certain embodiments, semi-metal and other metals comprise the mixture of silicon, boron, germanium, Shen, Antimony, tellurium, Tong, Magnesium, Manganese, zinc, lithium, Tie, Chrome, Vanadium, TA , Gallium, Xi , Zirconium, Nickel, Cobalt and above element.In certain embodiments, aluminium alloy comprise aluminium more than about 85%, more than the aluminium of about 87wt.%, more than about 90% aluminium, more than the aluminium of about 92wt.%, more than the aluminium of about 93wt.%, more than the aluminium of 94wt.%, or more than more than 95wt.%of aluminium, based on the gross weight of aluminium alloy.In certain embodiments, aluminium alloy comprises more than about 1wt.%, more than about 2wt.%, more than about 3wt.%, more than about 4wt.%, more than about 5wt.%, more than 6wt.%, or more than the non-aluminium component of 7wt.%, based on the gross weight of aluminium alloy.
[0039] in further embodiments, aluminium alloy is a kind of alloy that comprises aluminium and copper.In certain embodiments, aluminium alloy comprises copper more than about 1wt.%, more than the copper of about 2wt.%, more than the copper of about 3wt.%, more than the copper of about 4wt.%, more than the copper of about 5wt.%, more than the copper of 6wt.%, or more than the copper of 7wt.%, based on the gross weight of aluminium alloy.In certain embodiments, aluminium alloy does not contain copper substantially.
[0040] in other a little embodiment, aluminium alloy is that a kind of Lv of comprising is Ji the alloy of Magnesium.In certain embodiments, aluminium alloy comprises more than about 1wt.% De Magnesium, more than about 2wt.% De Magnesium, more than about 3wt.% De Magnesium, more than about 4wt.% De Magnesium, more than about 5wt.% De Magnesium, more than 6wt.% De Magnesium, or more than 7wt.% De Magnesium, based on the gross weight of aluminium alloy.In certain embodiments, aluminium alloy Han You Magnesium not substantially.
[0041] in other a little embodiment, aluminium alloy is that a kind of Lv of comprising is Ji the alloy of Manganese.In certain embodiments, aluminium alloy comprises more than about 1wt.% De Manganese, more than about 2wt.% De Manganese, more than about 3wt.% De Manganese, more than about 4wt.% De Manganese, more than about 5wt.% De Manganese, more than 6wt.% De Manganese, or more than 7wt.% De Manganese, based on the gross weight of aluminium alloy.In certain embodiments, aluminium alloy Han You Manganese not substantially.
[0042] in other a little embodiment, aluminium alloy is a kind of alloy that comprises aluminium and silicon.In certain embodiments, aluminium alloy comprises silicon more than about 1wt.%, more than the silicon of about 2wt.%, more than the silicon of about 3wt.%, more than the silicon of about 4wt.%, more than the silicon of about 5wt.%, more than the silicon of 6wt.%, or more than the silicon of 7wt.%, based on the gross weight of aluminium alloy.In certain embodiments, aluminium alloy does not contain silicon substantially.
[0043] in other a little embodiment, aluminium alloy is a kind of alloy that comprises aluminium and zinc.In certain embodiments, aluminium alloy comprises zinc more than about 1wt.%, more than the zinc of about 2wt.%, more than the zinc of about 3wt.%, more than the zinc of about 4wt.%, more than the zinc of about 5wt.%, more than the zinc of 6wt.%, or more than the zinc of 7wt.%, based on the gross weight of aluminium alloy.In certain embodiments, aluminium alloy does not contain zinc substantially.
[0044] in other a little embodiment, aluminium alloy is a kind of alloy that comprises aluminium and tin.In certain embodiments, aluminium alloy comprises tin more than about 1wt.%, more than the tin of about 2wt.%, more than the tin of about 3wt.%, more than the tin of about 4wt.%, more than the tin of about 5wt.%, more than the tin of 6wt.%, or more than the tin of 7wt.%, based on the gross weight of aluminium alloy.In certain embodiments, aluminium alloy does not contain tin substantially.
[0045] in certain embodiments, the aluminium alloy that is fit to be used for to form the described zone of oxidation of this specification sheets is forging aluminium alloy (wrought aluminum alloys).Generally speaking, the system of the available general identification alloying element of the identification of wrought aluminium: 4 bit digital, the back adds a dotted line, the letter of an expression type of heat treatment, and the numeral of representing one 1 figure place to 4 figure place of specific drawability (specific temper), as, 6061-T6 represents common easy-cutting aluminum alloy (free-machining aluminum alloy).The physicals of aluminium alloy can be by thermal treatment and specific temper influence.
[0046] non-limiting examples of some suitable forging aluminium alloys and composition thereof is listed in the table below in 1.
[0047] forging aluminium alloy known to any those skilled in the art all can be fit to form zone of oxidation disclosed in this invention.In some embodiment, aluminium alloy can be any alloy of 2000 series, 3000 series, 4000 series, 5000 series, 6000 series or 7000 series alloys.In general, the main non-aluminium composition of the aluminium alloy of 1000 series, 2000 series, 3000 series, 4000 series, 5000 series, 6000 series or 7000 series is respectively copper, manganese, silicon, magnesium, magnesium/silicon and zinc.The non-limiting examples of the forging aluminium alloy that some are suitable is listed in the table 1, and 2011,2017,4032,5005,6061 and analogue.
[0048] in other embodiment, therefore each aluminium alloy in 1000 series, 2000 series, 3000 series, 4000 series, 5000 series, 6000 series or 7000 series all can be allocated as follows identify codes (tempercode) such as described F, O, T or H by thermal treatment.
[0049] " F " yard state of representing alloy (fabricated) to come out for " forging ", that is, do not have in thermal treatment after forming process or the strain hardening process through similarly being controls especially such as casting (casting), hot-work (hot working), cold working (cold working).
[0050] on behalf of alloy, " O " sign indicating number advanced annealing.This represents minimum intensity, high-ductility temperature (ductility temper).
[0051] on behalf of alloy, " T " sign indicating number be reinforced through Overheating Treatment, no matter whether pass through strain hardening (strain hardening) afterwards." T " identify code comprises following several.
T1 is from the cooling of high-temperature molding process and weather aging stable status extremely substantially.
T2 is from the cooling of a high-temperature molding process, cold working and weather aging to stable status substantially.
The thermal treatment of T3 solution, cold working, and weather aging is to stable status substantially.
The thermal treatment of T4 solution, and weather aging is to stable status substantially.
T5 cools off temper(ing) then from a high-temperature molding process.
T6 solution thermal treatment temper(ing) then.
The thermal treatment of T7 solution is overaging/stabilization then.
The thermal treatment of T8 solution, cold working, temper(ing) then.
The thermal treatment of T9 solution, temper(ing), cold working then.
T10 is from the cooling of a high-temperature molding process, cold working and temper(ing).
Whether [0052] " H " sign indicating number is represented alloy overstrain sclerosis and is reinforced, no matter afterwards through Overheating Treatment." H " strain hardening identify code comprises following several.
H1 has only strain hardening.
H2 strain hardening and part annealing.
H3 strain hardening and stabilization.
H4 strain hardening and spray paint (lacquered) or paint (painted).Suppose the heat effect of coating process
Can influence strain hardening.This is not frequent generation.
[0053] in some embodiment, the aluminium alloy that is fit to be used for to form zone of oxidation is cast aluminium alloy (cast aluminum alloys).Generally speaking, cast aluminium can add that the system of a radix point discerns with 4 to 5 bit digital.The representative of the place of hundred bit digital be element as alloy, and its form of the digitized representation of radix point back, for example cast appearance shape or ingot bar (ingot).As, cast aluminium alloy comprises x1xx.x series, it comprises at least 99% aluminium; Wrap copper bearing x2xx.x series; The x3xx.x series that comprises silicon, copper and/or magnesium; The x4xx.x series that comprises silicon; Wrap magniferous x5xx.x series; Wrap zinciferous x7xx.x series; Wrap stanniferous the x8xx.x series; With the x9xx.x series that comprises other metals.The non-limiting examples of the forging aluminium alloy that some are suitable comprises 355,356,357,360,380,319 and analogue.
[0054] in some embodiment, the aluminium alloy that is fit to be used for to form zone of oxidation is the aluminium alloy of being named.The non-limiting examples of some named aluminium alloys comprises Al-Li alloy (alloy of aluminium and lithium), duralumin (Duralumin, the alloy of aluminium and copper), Nambe (aluminium adds 7 kinds of other metals that are not disclosed), Magnox (alloy of aluminium and magnesium), Zamak (alloy of aluminium, zinc, magnesium, copper), Silumin (alloy of aluminium and silicon) and AA-8000.
[0055] in general anode oxidation method disclosed in this invention comprises at least three steps, that is, and and pre-treatment, anodic oxidation and aftertreatment.Preprocessing process known to any those skilled in the art all can be used as the pre-treatment on the preceding aluminum surface of anodic oxidation step.The non-limiting examples of the preprocessing process that some are fit to comprise with machinery and/or chemical process purify the surface, with corona discharge (corona discharge), flame, plasma, alkalescence and/or acid etching or blended method treat surface.In some embodiment, the surface of aluminum can be cleaned earlier by chemical treatment or etching.Purification can be via the mixing of any known mechanical means, chemical process or above method.The infinite embodiment of a purification is included in and uses solution to remove lip-deep oil and particle in the oil removing process of using mechanical stirring or ultrasonic vibration.
[0056] optional, the surface of purification can continue with the alkaline earth metal solution of no etching in addition chemical treatment can preferably at high temperature carry out with further removal pollutent.Perhaps, the aqueous solution etching in addition of the mixture of mineral acid, strong organic acid or above article can be used in the surface of purification.The non-limiting examples of the mineral acid that some are suitable comprises the mixture of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, Hydrogen bromide, hydroiodic acid HI, phosphoric acid and above article.The non-limiting examples of some appropriate organic comprises the mixture of tosic acid, trifluoroacetic acid, 4-trifluoromethylbenzoic acid, methylsulphonic acid, acetic acid and above article.The etching acid solution can further comprise an oxygenant for example metal dichromate (metal dichromates) (as lithium, sodium, potassium dichromate) or metal permanganate (metal permanganates) (as lithium, sodium, potassium permanganate), the mixture of superoxide (as hydrogen peroxide) and above article.
[0057] in general, can control etched degree (promptly slightly, moderate, severe) by time that changes etching process and temperature.The etched time can be from about 5 minutes to about 4 hours, from about 10 minutes to about 2 hours, or change between from about 15 minutes to about 1 hour.Etched temperature range can be about 20-90 ℃, about 25-80 ℃, about 30-75 ℃, or about 30-60 ℃.In general the increase of etched degree can increase by increasing etched time, etched temperature or above method blended mode.
[0058] in some embodiment, pre-treatment can be carried out by ForestProduct Laboratories (FPL) etching process in the surface of aluminum.In general the FPL etching process comprises following steps:
1) deoiling step uses for example hydrocarbon polymer or halogenated hydrocarbon, and promptly trieline (trichloroethylene) equal solvent removes lip-deep oil and particle;
2) alkaline-earth metal purifying step under about 50-80 temperature, is immersed in non-etching alkaline earth metal solution with further removal pollutent with aluminum;
3) etching step was immersed in aluminum in sulfuric acid and the sodium dichromate aqueous solutio about 9-15 minute;
4) cleaning step cleaned aluminum about 1-2 minute with water not being higher than under 50 ℃ the temperature; With
5) drying step be not higher than under 65 ℃ the temperature with the dry air aluminum about one hour.
[0059] in other embodiment, (phosphoric acid anodize, PAA) etching process comes pre-treatment with phosphoric acid anodizing on the surface of aluminum.The PAA etching process is in general similar to the FPL etching process, just the PAA etching process further comprises an anode oxidation process, the bias voltage that described anode oxidation process comprises an about 10V imposes on the stainless steel cathode, to produce a surperficial anode layer (superficial anodiclayer) on workpiece.
[0060] alternatively, can come the surface of pre-treating aluminium material to make its brightization with spissated phosphoric acid and nitrate mixture.In some embodiment, can produce the effect of approximate minute surface.
[0061] in the anodic oxidation step, aluminum is immersed in the water-bath that contains electrolytic solution, allows electric current generate a zone of oxidation by described water-bath with the surface at aluminum simultaneously.Described zone of oxidation is mainly from aluminum itself, but not from described electrolytic solution.According to different aluminums, zone of oxidation can be transparent, opaque or colored.In addition, zone of oxidation can simultaneously or be colored afterwards, produces one or more needed colors, uses to be applicable to various decorations and/or protectiveness.
[0062] in general electrolytic solution comprises water, sulfuric acid and oxalic acid.Any commercial obtainable sulfuric acid all can use.The vitriolic consumption can be that every liter of electrolytic solution contains about 100-360 gram, about 140-220 gram or about 160-200 gram.Any commercial obtainable oxalic acid all can use.The content of oxalic acid can be that every liter of electrolytic solution contains about 5-40 gram, about 12-20 gram, or about 14-18 gram.In some embodiment, the sulfuric acid content of every liter of electrolytic solution restrains for about 160-200 and every liter of electrolytic solution contains the about 14-18 gram of oxalic acid.
[0063] alternatively, described electrolytic solution can further comprise the mixture of the organic acid of aluminum ion, metal sulfate, a kind of non-oxalic acid, a kind of metallized metal carboxylate salt or above article.In some embodiment, described electrolytic solution comprises aluminum ion.Aluminum ions content can be that every liter of electrolytic solution contains about 0.5-30 gram, about 1-20 gram, or about 2-11 gram.In other embodiment, described electrolytic solution comprises organic acid or a kind of organic acid metal-salt of a metal sulfate or a kind of non-oxalic acid.Each content of metal sulfate, organic acid and metal carboxylate can be that every liter of electrolytic solution contains 0 gram to about 100 grams.In some embodiment, described electrolytic solution is the organic acid of containing metal vitriol, non-oxalic acid not substantially, or metal carboxylate.
[0064] non-limiting examples of some metal sulfates comprises the vitriol of the mixture of lithium, sodium, potassium, copper, magnesium, manganese, silicon, zinc, iron, chromium, vanadium, titanium, bismuth, gallium, tin, lead, zirconium, nickel, cobalt or above article.Some organic acid non-limiting examples that are fit to comprise representative examples of saturated aliphatic α hydroxyl monoprotic acid (saturated aliphatic alpha-hydroxymonocarboxylic acids), saturated and unsaturation aliphatic dicarboxylic acid (aliphatic dicarboxylic acid) as oxyacetic acid (glycolic acid), lactic acid (lacticacid) and oxysuccinic acid (malic acid) and non-oxalic acid, as propanedioic acid (malonic), succsinic acid (succinic), and toxilic acid (maleic acid).The metal of metal carboxylate can be lithium, sodium, potassium, copper, magnesium, manganese, silicon, zinc, iron, chromium, vanadium, titanium, bismuth, gallium, tin, lead, zirconium, nickel or cobalt.Described carboxylate salt can derive from representative examples of saturated aliphatic α hydroxyl monoprotic acid, representative examples of saturated aliphatic α hydroxyl monoprotic acid and saturated and unsaturation aliphatic dicarboxylic acid, comprises the mixing of oxalic acid or above article.
[0065] temperature of anodic oxidation water-bath can be about 5-25 ℃ or about 10-15 ℃.The density of first electric current in first time phase of described anodic oxidation step can be less than 0.7A/dm
2, less than 0.6A/dm
2, or less than 0.5A/dm
2The about 1.5-2.5A/dm of density with second electric current in second time phase
2, about 1.6-2.4A/dm
2, or about 1.7-2.3A/dm
2First time phase can be from 0-10 hour, about 0.5-5 hour, or about 1-1 hour.Second time phase can be about 1-5 hour, about 5-1.5 hour, or about 5-45 minute.Described anodic oxidation step can further be included in and use the 3rd electric current, the about 0.5-2.0A/dm of its current density in the 3rd time phase
2, about 0.75-1.75A/dm
2, or about 1.0-1.5A/dm
2The 3rd time phase can be about 1-5 hour, about 1-2 hour, or about 1-30 minute.
[0066] desire remains on current density in the specific scope, can increase the about 10-250 volt of the voltage that puts on the electrode gradually along with the time, depends on the zone of oxidation that generates on the aluminum and decides.In some embodiment, the about 10-200 volt of the voltage range that is applied, about 15-150 volt, or about 20-100 volt are with the holding current density constant or in a specific scope.Described anodic oxidation step can be used the mixing of constant DC stream galvanic current, pulse direct current electric current, commutating pulse galvanic current, alternating current, rectification alternating current or an above electric current.
[0067] alternatively, described electrolytic solution can utilize any stirring or refrigerating unit to stir or cooling, to remove the heat that generates in the anode oxidation process on the aluminum surface.The temperature of electrolytic solution is effectively controlled the physicals that can make the film quality stabilization and improve film.In some embodiments, whipping appts can be the mechanicalness mixing device, for example agitator, stirrer, homogenizer, or vibration of ultrasonic wave device or stirrer etc. can promote electrolytic solution at aluminum near surface mobile device.
[0068] in other embodiment, whipping appts comprises one or more mixing drums that contain the hole, the about 5-50 micron of the diameter in described hole, about 10-40 micron, or about 15-25 micron.Air can be compelled to by these holes, to produce very fine bubble on the surface of aluminum.These bubbles can be with the thermal energy transfer that produces on the surface of aluminum to the comparatively cryogenic part of electrolytic solution.
[0069] described porous anodic oxide coating can be colored or painted, sealing, polishing, or the mixing of above method.In some embodiment, described zone of oxidation can dye earlier and seal, to form a dye coating thereon.Organic and the inorganic dyestuff or the pigment of any suitable dyeing anodic oxidation zone of oxidation all can use.Fig. 1 shows the hole (2) of the anode unit (1) of the anodic oxide coating on the aluminum base layer (3).In some embodiment, the diameter of hole is about 0.005-0.05 micron, or about 0.01-0.03 micron.In other embodiment, the particle diameter of dyestuff or pigment molecular is about 5-60 nanometer, or the 15-30 nanometer.Dyeing or colorize method known to dyeing or painted available any those skilled in the art make dyestuff or color enter or be deposited on hole on the anode unit, to form a dye coating.
[0070] some organic and inorganic dyestuff all has description on document, and for example, at S.Kawai, " Anodizing and Coloring of Aluminum Alloys, " ASMInternational (2002) incorporates this specification sheets at this into way of reference.Some organic dye non-limiting examples comprise matching stain, acid metal complex dye, acidic medium dyestuff, substantive dyestuff, weak acid dye, dispersed dye, decomposition-reduction dyestuff, reactive dyestuffs, alkaline-earth metal dyestuff and solvent dye, for example dissolve in the dyestuff oil-soluble colourant of alcohol.The non-limiting examples of some inorganic dyestuffs is listed in the table below 2.The color that obtains from inorganic dyestuff also is listed in the table below 2.
Table 2.
[0071] generally speaking, dyeing or painted can reaching via following method.In electrocolor process, after the anodic oxidation, workpiece is dipped in the water-bath that contains inorganic metal salt, applies electric current afterwards and makes metal-salt be deposited on the bottom of hole.The color that generates is relevant with the condition of used metal and process.In addition, the scope of color can be by organic dye is enlarged with overstaining step.The non-limiting examples metal of some suitable metals comprises tin, cobalt, nickel and copper.
[0072] integral colouring (integral coloring) combines anodic oxidation and painted, simultaneously the wall of oxide unit formed and to be coloured to bronze-colored and black shade (blackshades).It can be one of the most expensive process, because it need show the more electric power that lands.
[0073] organic dyeing can be used for producing the color of many types.These organic dye provide lively color, its intensity perhaps be on the market other pigment system can not compare.Generally speaking, they can provide splendid weather resistance and light resistance.And can enlarge the scope of color by the electrolysis color is overstained with organic dye, make it have a greater variety of colors and shade.This method is relatively cheap, and required initial cost is minimum in all coloring process.
[0074] disturbs painted (interference coloring) to comprise and be modified at the hole structure that produces in the vitriolated electrolytic solution.The expansion of hole can occur in the bottom of hole.The metal that is deposited on these positions can produce the color of many tool light resistance, from blue, green and yellow to redness.Described color is caused by optical interference usually, but not the basic used light scatter of electrolytic coloring process.
[0075] in some embodiment, the hole that organic dye is used to insert anodic oxide coating reaches painted purpose.In other embodiments, inorganic dyestuff or metallic salt can be deposited into the bottom of hole to generate shades of colour through electrochemical method.In other embodiment, a metal (as tin) can by electrolytic deposition in the hole of anodic oxide coating so that color to be provided.In specific embodiment, can use pulsed current to sulfuric acid electrolyte with in oxidising process by adding specific organic acid, integrate ground and generate described color on anodic oxide coating or inner.The non-limiting examples of some zone of oxidation colors comprises the known shade and the tone of redness, orange, yellow, green, blue, indigo look, purple, pink, silver color, gold, bronze-colored, brown, black, grey, champagne, white and all these colors.
[0076] after the dyeing, the surface of described zone of oxidation can be sealed alternatively, and available method known to those skilled in the art seals anodic oxide coating.In general, sealing is the sealing of the hole of anode unit, therefore can provide one can antipollution, wearing and tearing, friction, and the surface of color degradation.Moreover chance and the increase erosion resistance that dyestuff overflows can be lowered or eliminate to sealing.In some embodiment, carry out in the described salt that is sealed under 20 ℃, as nickel salt, the mixture of cobalt salt and above article is with described salt penetration and cap holes.In other embodiment, sealing utilizes hot water or steam to become the form of hydrated form to carry out oxygenate conversion.Described conversion can reduce the size of the hole of anode unit, and therefore, along with oxide compound expands, the porousness (porosity) on surface decreases.In other embodiments, can under the situation of metal dichromate such as sodium dichromate 99 existence, seal.In other embodiments, can under the situation of metal acetate salt such as nickel acetate or other anti-flower agent (anti-bloom agent) existence, seal.
[0077] after the sealing, can optionally the surface of zone of oxidation be polished or polishing with method known to those skilled in the art.In some embodiment, polish or polishing with compound with polishing or polishing on the surface of zone of oxidation.Polishing or polishing comprise the additive that polishing particles, binding agent and selectivity are added usually with compound.Polishing or polishing can further comprise dilution with particle for example marble, gypsum, flint, tripoli, ferric oxide, pure aluminium silicate and glass (comprising glass envelope and granulated glass sphere) with compound.Polishing or polishing can be pie, tubulose, paste or aqueous with the profile of compound.Some polishings or polishing comprise that with the non-limiting examples of compound the oyster white of taking from French Rhone-Poulenc Co. company polishes with compound (Opaline polishingcompound) and take from the tripoli compound (tripoli compound) of Michigan, United States Formax Manufacturing Corp. company.
[0078] any traditional polishing particles known in the art all can be used as polishing or polishing compound.The non-limiting examples of some polishing particles comprises the molten aluminum oxide compound, white fused alumina (white fused alumina) for example, thermal treatment aluminum oxide and brown aluminum oxide), silicon carbide (silicon carbide), green silicon carbide for example, norbide, titanium carbide, diamond, cubic boron nitride (cubic boron nitride), garnet (garnet), tripoli (tripoli, microcrystalline silica), chromic oxide, cerium oxide (cerium), molten aluminum zirconium (fused alumina-zirconia), the mixture of sol-gel method synthetic polishing particles (sol-gel-derived abrasive particles) and above article.Any traditional polishing compound binding agent known in the art all can be used as polishing or polishing compound.The non-limiting examples of the binding agent that some are fit to comprises natural wax, synthetic wax, chlorinated wax, as the mixture of tetrahedronaphthalene (tetrachloronaphtalene), five chlorinated naphthalenes (pentachloronaphthalene), polyvinyl chloride (polyvinyl chloride) and above article.
[0079] any traditional interground addition known in the art all can be used as polishing or polishes the purposes of using compound.The non-limiting examples of the additive that some are fit to comprises the pigment (pigment) as titanium dioxide, or the mixture of ferric oxide, emulsifying agent, interfacial agent, wetting agent, suds-stabilizing agent, heating power or ultra-violet stabilizer, antioxidant, abrasive and above article.The embodiment of abrasive comprises Organohalogen compounds, halide salt, as sodium-chlor, potassium cryolite (potassium cryolite), sodium cryolite (sodium cryolite), ammonium sodium aluminum fluoride (ammonium cryolite), potassium fluoborate (potassium tetrafluoroboate), Sodium tetrafluoroborate (sodium tetrafluoroborate), silicon fluoride (siliconfluorides), Repone K (potassium chloride) and magnesium chloride (magnesiumchloride).
[0080] in some embodiment, can contact with workpiece surface with the rotary finishing wheel that polishing compound is housed and polish.In other embodiment, polishing can be carried out in two steps suddenly, promptly cuts (cutting down) and painted (coloring).Cutting step is initial step, carries out with the coarse burnishing compound that cuts.In some cases, cutting step may be to reach surface luster or the required unique step of smoothness.Painted step generally comprises slight polishing, and is glossy to bring workpiece surface.Preferably, can use coloring compound.Compared with the polishing compound that is used to cut step, some coloring compounds contain the less abrasive material of mesh size.
[0081] in some embodiment, polishing compound is to be aqueous or paste.The polishing particles of making aqueous or paste is identical with the polishing particles that is used for the solid polishing compound usually with binding agent.Bring composition aqueous or the paste polishing compound into an emulsive, water base fluid is as application such as spraying or brushings.
[0082] in some specific embodiments, polishing is to reach by polishing wheel.Polishing wheel generally provides two major functions.First function is that polishing particles is brought to the surface of workpiece to cut and/or painted action.Second function then is when needs, produces enough heat of friction, with the effect that produces plastic flow (plastically flowing) or polish (burnishing) at workpiece surface.Known to various those skilled in the art, the polishing wheel with different designs and structure all can be used for polishing required for the present invention and polishing process.
[0083] in other embodiment, for example meticulous grinding abrasive disk or dry sanding paper can be polished with the sand milling agent known to those skilled in the art, frosted compound or other frosted things in the surface of zone of oxidation.In some embodiments, the surface of zone of oxidation is to polish with little polishing product, for example polished film (lapping film).In some embodiments, to comprise granularity be 400 or above frosted thing to polished film.In some embodiment, zone of oxidation has a surface roughness Ra value and is less than about 0.1 micron, is less than about 0.09 micron, is less than about 0.08 micron, is less than about 0.07 micron, is less than about 0.06 micron, is less than about 0.05 micron, is less than about 0.04 micron, is less than about 0.03 micron, is less than about 0.02 micron, or is less than about 0.01 micron.Surface smoothness can be measured with following technology of profiling (Profilometry method).
[0084] described zone of oxidation surfaceness can record available from Talysurf PGI 1240 aspherical measuring systems of Britain Taylor Hobson.Gauge can be about 10 millimeters, about 5 millimeters, about 1 millimeter, about 0.5 millimeter, about 0.25 millimeter or about 0.1 millimeter.Probe speed during measurement can be about 5 mm/second, about 1 mm/second, about 0.5 mm/second, about 0.25 mm/second or about 0.1 mm/second.
[0085] in some embodiment, micron hardness (microhardness) value about 280-1000Hv, about 280-750Hv of described zone of oxidation, about 300-550Hv, about 320-520Hv, or about 320-500Hv, can measure and get by the method disclosed in the present.In an embodiment, described micron hardness can record with BuehlerMicromet 2103 methods, comprises the Vickers diameter pressure head (Vickers diameter) of Disk formula (square base) Di the Fang with 136 degree.In another concrete embodiment, described micron hardness can record with the method for measuring micron hardness known to any those skilled in the art.
[0086] in some embodiment, the about 15-100 micron of described thickness of oxide layer, about 15-75 micron, about 15-50 micron, about 15-40 micron or about 15-30 micron.In an embodiment, thickness can be recorded by Fischer film thickness test machine.
[0087] the method disclosed in the present can be used as and does anodic oxidation in batches and continuous coil (continuous coil) anodic oxidation.In general anodic oxidation comprises bracket component in batches, they can be immersed a series of treatment trough.Some suitable non-limiting examples of anodised parts in batches comprise the aluminium parts of metal parts, castings, kitchen utensils, cosmetic container, flash of light lamp body and the mechanize of extruding part, thin slice or bending.
[0088] in general the continuous coil anodic oxidation comprises via a series of anodic oxidation coil, etching and the purification tank spooled in advance of turn-off continuously, rolls anodised coil afterwards again with shipment and forging.This method can be used in a large amount of thin slices, paillon foil and comparatively simple product, for example spacer bar of light fixture, reflector, blind window, insulating glass and roofing (continuous roofing) system continuously.
Embodiment
[0089] just as explaining orally purposes, not in office where face limits the scope of the invention the following example.
Embodiment 1
[0090] embodiment 1 prepares according to following steps: anode aluminium oxide alloy Al-6063 workpiece under the temperature of the electrolytic solution that contains water, sulfuric acid (180 gram/litre electrolytic solution) and oxalic acid (16 gram/litre electrolytic solution) and about 10-16 ℃.Described anode oxidation process is finished with four steps in order, and each step comprises different current densities and electrolysis time.The current density of first step is 0-0.7A/dm
2, kept 10 minutes.The current density of second step is about 0.7-2.0A/dm
2, kept 10 minutes.The current density of the 3rd step is about 2.0-2.5A/dm
2, kept 10 minutes.The current density of the 4th step is about 1.5-2.5A/dm
2, kept 50 minutes.Current density is to be produced by a pulsed galvanic current (DC) with volt about 20-24V of voltage.First, second, third pulsed current sequence is out to close 0.2 second after 0.8 second.The 4th pulsed current sequence is out to close 0.4 second after 0.6 second.、
Embodiment 2
[0091] embodiment 2 is that just workpiece is dyed blueness according to step preparation similar to Example 1.
[0092] embodiment 3 is that just workpiece is dyed redness according to step preparation similar to Example 1.
Comparative Examples A
[0093] Comparative Examples A is to prepare according to following steps: under electrolytic solution that contains water, sulfuric acid (180-200 gram/litre electrolytic solution) and about 24 ℃ temperature, and with voltage 12-22V, the about 1.0A/dm of current density
2About 15 minutes of direct current anodised aluminium alloy A l-6063 workpiece.
Comparative example B
[0094] comparative example B prepares according to following steps: under electrolytic solution that contains water, sulfuric acid (180-200 gram/litre electrolytic solution) and about 24 ℃ temperature, and with voltage 12-22V, the about 1.0A/dm of current density
2Direct current anodised aluminium alloy A l-6063 workpiece about 45-60 minute.
Comparative example C
[0095] comparative example C prepares according to following steps: carbon and physical vapor evaporation coating technique with a similar diamond plate film with aluminium alloy Al-6063 workpiece.During the process about 2-2.5 hour.General about 1 micron of the thickness of the carbon film of similar diamond.The interface is a chromium.
Comparative example D(the second class anodic oxidation)
[0096] comparative example D prepares according to following steps: under the temperature of the electrolytic solution that contains water, sulfuric acid (190-200 gram/litre electrolytic solution) and about 18-20 ℃, and with voltage 15-17V, the about 1.5A/dm of current density
2Direct current anodised aluminium alloy A l-6063 workpiece about 45-60 minute.
Wearing test
[0097] wearing test is to be used for the abrasion resistance of test comparison embodiment A-C and embodiment 1.Described wearing test be with Taber grinding loss test machine (Abrasive WearingTester) according to the ISO5470-1 step, utilize the frosted head of CS-17 load 1Kg to finish.Described test is carried out opening under the suction unit, and speed is 40rpm.Thickness of oxide layer is recorded by Fischer film thickness test machine.Described Wear Test Data is listed in the table below 3.The antiwear property comparison of the data presentation embodiment 1 of table 3 is than embodiment A-C height.
Table 3. wearing test result
The hardness test of film micron
[0098] the micron hardness of comparative example D and embodiment 1 is tested.Micron hardness test machine is Buehler Micromet 2103 test machines with Vickers diameter pressure head (Vickers diameter) of Disk formula (square base) Di the Fang of 136 degree.Comparative example D and embodiment 1 are settled (plastic mounted) and polishing by crosscut, plasticity before measurement.As for the load of micron hardness test machine, embodiment 1 is 300gf, comparative example D500gf.Micron hardness test data are listed in the table below 4 and 5.The average micron hardness ratio comparative example D height of table 4 and 5 data presentation embodiment 1.
The micron hardness test result of table 4. embodiment 1
The micron hardness test result of table 5. comparative example D
| Test load (gf) | Micron hardness (HV) | Note |
| 500 | 267.7 | Film breaks |
| 500 | 258.8 | Film breaks |
| 500 | 272.2 | Film breaks |
| On average | 266.2 | Unpredictable |
[0099] embodiment 2 and 3 surfaceness are to record with Talysurf PGI 1240 aspherical measuring systems available from Britain Taylor Hobson.Gauge is about 0.25 millimeter.Probe speed during measurement is 0.5 mm/second.Used strainer is the ISO type.Each sample all with to the east of the west, reach in the south north directional survey.Embodiment 2 and 3 surface roughness data are listed in the table below 6.
Table 6.
| Sample | To the east of the west to the Ra value | Reach in the south the north to the Ra value | Average Ra |
| Embodiment 2 | 0.038 micron | 0.040 micron | 0.039 |
| Embodiment | |||
| 3 | 0.038 micron | 0.041 micron | 0.040 micron |
[00100] as implied above, embodiments of the invention provide several different methods to produce the colored oxide layer that is used for decorative use.Though the present invention describes with a limited number of embodiment, the particular feature of each embodiment should not be regarded as the feature of other embodiment.None embodiment can represent all aspects of the present invention.In certain embodiments, described method can comprise the step that several are not mentioned.In other embodiments, described method does not comprise, or does not contain the step of not mentioning substantially.Described embodiment also can change or modify a little.It should be noted that the method that produces colored oxide layer is to describe with several steps.The enforcement order of these steps can conversion.Wherein one or more steps can be omitted or be merged, and still can reach identical substantially result.Claims then wish to cover all variation and modifications in the scope of the invention.
[00101] this specification sheets is all intactly included in mentioned publication and the patent application of all these specification sheetss by reference in, all is included into this specification sheets with way of reference as each part publication and patent application with naming especially.Though understand the present invention in order to know, above-mentioned invention is made detailed explanation in the mode of embodiment, those skilled in the art can make change or modification to the present invention easily, and not depart from the scope or the spirit of claims in instruction of the present invention.
Claims (20)
1. method that produces colored oxide layer on aluminum comprises following steps:
(a) placing described aluminum comprises in water, oxalic acid, the vitriolic electrolytic solution as anode in one; With
(b) the described aluminum of anodic oxidation is less than about 0.8A/dm with current density earlier
2The described aluminum of first galvanic anode oxidation about 1-60 minute; Again with the about 1.5-2.5A/dm of current density
2Second described aluminum of galvanic anode oxidation, to produce a zone of oxidation.
2. the process of claim 1 wherein that described aluminum further is about 1.0-1.5A/dm by current density
2The 3rd galvanic anode oxidation.
3. the method for claim 2, wherein said first, second, third electric current produced by Constant Direct Current electric current or pulse direct current electric current respectively.
4. the method for claim 1 further comprises the step that stirs described electrolytic solution with an agitator.
5. the method for claim 4, wherein said agitator comprises several mixing drums.
6. the method for claim 1 further is included in the step that forms a dye coating on the described zone of oxidation.
7. the process of claim 1 wherein that described electrolytic solution further comprises the mixture of aluminum ion, metal sulfate, organic acid or above article.
8. the process of claim 1 wherein that described electrolytic solution further is included in the aluminum ion of about 2-11 gram in every liter of electrolytic solution.
9. the process of claim 1 wherein that described electrolytic solution is included in the oxalic acid of 5-40 gram in every liter of electrolytic solution and about 100-360 gram sulfuric acid in every liter of electrolytic solution.
10. the method for claim 9, wherein said electrolytic solution be included in every liter of electrolytic solution about 12-20 gram oxalic acid and in every liter of electrolytic solution about 140-220 restrain sulfuric acid.
11. the method for claim 10, wherein said electrolytic solution are included in, and about 14-18 restrains oxalic acid and about 160-200 gram sulfuric acid in every liter of electrolytic solution in every liter of electrolytic solution.
12. the process of claim 1 wherein that described anodic oxidation step carries out under about 5-25 ℃ temperature.
13. the method for claim 12, wherein said anodic oxidation step is carried out under about 10-15 ℃ temperature.
14. the process of claim 1 wherein that described step further comprises the described zone of oxidation of polishing surface to Ra value and is less than about 0.1 micron.
15. an object comprises aluminum, has a colored oxide layer on the described aluminum, the preparation method of wherein said zone of oxidation comprises following steps:
(a) placing described aluminum comprises in water, oxalic acid, the vitriolic electrolytic solution as anode in one; With
(b) the described aluminum of anodic oxidation is less than about 0.8A/dm with current density earlier
2The described aluminum of first galvanic anode oxidation about 1-60 minute; Again with the about 1.5-2.5A/dm of current density
2Second described aluminum of galvanic anode oxidation, to produce a zone of oxidation.
16. the object of claim 15, wherein said colored oxide layer have the micron hardness value of about 280-1000Hv.
17. the object of claim 15, wherein said colored oxide layer has the thickness of about 15-50 micron.
18. the object of claim 15, wherein said aluminum comprises aluminium and an element of optionally being chosen, and described element is selected from the group of being made up of the mixture of silicon, boron, germanium, arsenic, antimony, tellurium, copper, magnesium, manganese, tin, lithium, iron, chromium, vanadium, titanium, bismuth, gallium, tin, lead, zirconium, nickel, cobalt and above element.
19. the object of claim 15 further comprises a dye coating on the zone of oxidation.
20. the object of claim 15, the surface of wherein said colored oxide layer have the Ra value of about 0.01-0.1 micron.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/744,829 US20080274375A1 (en) | 2007-05-04 | 2007-05-04 | Anodizing Aluminum and Alloys Thereof |
| US11/744,829 | 2007-05-04 |
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| Publication Number | Publication Date |
|---|---|
| CN101298690A true CN101298690A (en) | 2008-11-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101020534A Pending CN101298690A (en) | 2007-05-04 | 2007-05-10 | Anodizing aluminium and alloys thereof |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20080274375A1 (en) |
| EP (1) | EP1980651A3 (en) |
| KR (1) | KR20080098331A (en) |
| CN (1) | CN101298690A (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP1980651A3 (en) | 2010-04-28 |
| EP1980651A2 (en) | 2008-10-15 |
| US20080274375A1 (en) | 2008-11-06 |
| KR20080098331A (en) | 2008-11-07 |
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